Certain 2-(2-substituted benzoyl)-4-(substituted oxy or substituted thio)-1,3-cyclohexanediones

ABSTRACT

Compounds of the formula ##STR1## wherein X is oxy, thio, sulfinyl or sulfonyl; 
     R is hydrogen; C 1  -C 2  alkyl; C 1  -C 2  alkoxy; trifluoromethyoxy; difluoromethoxy; nitro; cyano; C 1  -C 2  haloalkyl; R a  SO n  --wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl, trifluoromethyl or difluoromethyl; 
     R 1  is hydrogen, C 1  -C 4  alkyl, phenyl or substituted phenyl; 
     R 2  is hydrogen or C 1  -C 4  alkyl; or 
     R 1  and R 2  together are C 2  -C 5  alkylene; 
     R 3  is hydrogen, C 1  -C 4  alkyl, phenyl or substituted phenyl with the proviso that R 1  and R 3  are not both phenyl or substitute phenyl; 
     R 4  is hydrogen or C 1  -C 4  alkyl; 
     R 5  is hydrogen, or C 1  -C 4  alkyl; 
     R 6  is hydrogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, or phenyl; 
     R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  --wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)--wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; or (12) --SO 2  NR c  R d  wherein R c  and R d  are as defined; and (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; and their salts.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 086,268, filed Aug. 20, 1987, which is a continuation-in-part of application Ser. No. 919,280, filed Oct. 16, 1986 now abandoned.

BACKGROUND OF THE INVENTION

European patent application Nos. 135,191; 186,118, 186,119 and 186,120 relate to certain herbicidal compounds that can have the following structural formula ##STR2## wherein R through R⁵, R⁷ and R⁸ are substantially as defined below and R^(a) is C₁ -C₄ alkyl.

DESCRIPTION OF THE INVENTION

This invention relates to 2-(2-substituted benzoyl)-4-(substituted oxy or substituted thio)-1,3-cyclohexanediones and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(2-substituted benzoyl)-4-(substituted oxy or substituted thio)-1,3-cyclohexanedione and an inert carrier therefor. The 5- and 6-positions of the 1,3-cyclohexanedione moiety are preferably substituted with groups hereinafter defined, most preferably with hydrogen or methyl groups. The substituted benzoyl and cyclohexanedione moieties can be further substituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compounds having the following structural formula ##STR3## wherein X is oxy, thio, sulfinyl or sulfonyl;

R is halogen, preferably chlorine or bromine; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl, trifluoromethyl or difluoromethyl. Preferably, R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R¹ is hydrogen; C₁ -C₄ alkyl, preferably methyl; phenyl; or substituted phenyl;

R² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R¹ and R² together are C₂ -C₅ alkylene;

R³ is hydrogen; C₁ -C₄ alkyl, preferably methyl; phenyl; or substituted phenyl with the proviso that R¹ and R³ are not both phenyl or substituted phenyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁵ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, or phenyl and

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or

(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

Preferably R⁷ is in the 3-position. More preferably R⁷ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄ thioalkyl. Most preferably, R⁷ is hydrogen. Preferably R⁸ is in the 4-position. Most preferably R⁸ is halogen, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of this invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR4## wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and X are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR5## wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and X are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees of association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds or their salts to the area where control is desired.

The compounds of the present invention can be prepared by the following two-, or, if necessary, a three-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2), or, if necessary, by subsequent oxidation of the product obtained in step (2) as shown in reaction (3).

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR6## wherein R through R⁸ and X and moderate base are as defined and Y is halogen, preferably chlorine, C₁ -C₄ alkyl--C(O)--O--, C₁ -C₄ alkoxy--C(O)--O-- or ##STR7## wherein R, R⁷ and R⁸ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR8## wherein the moderate base and R through R⁸ and X are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.01-0.1 mole of the cyanide source. The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

Alternatively, certain compounds of this invention can be prepared by the following reaction: ##STR9## wherein R through R⁸ are as defined, m is the integer 1 or 2 and [O] is an oxidizing agent, preferably a peroxide such as peracetic acid or m-chloroperbenzoic acid.

Generally, in reaction step (3) the substituted thio is dissolved in methylene chloride and an oxidizing agent such as m-chloroperbenzoic acid (1.1 or 2.2 equivalents) is added portionwise and the reaction mixture is stirred for 1 to 8 hours. The product may be isolated using conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; benzaldehyde cyanohydrin; cyanohydrins of C₂ -C₅ aliphatic aldehydes such as acetaldehyde cyanohydrin, propionaldehyde propionaldehyde cyanohydrin, etc.; cyclohexanone cyanohydrin; lactonitrile; zinc cyanide; di- and tri-(lower alkyl)silyl cyanides, notably dimethyl- and trimethyl-silyl cyanide; potassium ferric cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as N,N-dimethylaniline (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I. L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR10## wherein R, R⁷ and R⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR11## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR12## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR13## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The substituted 1,3-cyclohexanediones can be prepared by a wide variety of general methods according to the teachings of Modern Synthetic Reactions, 2nd Edition, Chapter 9, H. O. House, W. A. Benjamin, Inc., Menlo Park, CA (1972).

The following examples teach the synthesis of a representative compound of this invention.

EXAMPLE 1 4-Methylthiocyclohexane-1,3-dione ##STR14##

1-(Methylthio)-2-propanone [25 grams (g), 0.24 mole], ethyl acrylate (24 g, 0.24 mol), and benzyltrimethylammonium methoxide [2 milliliters (ml) of 40 wt % solution in methanol] were dissolved in toluene (100 ml). To the solution was then added a solution of sodium methoxide (77.8 g of 25 wt % in methanol, 0.36 mol) dropwise at a rate as to maintain the temperature below 35° C. After stirring an additional 2 hours at room temperature, the reaction mixture was poured into 200 ml of ice water and extracted with 100 ml of ether. The aqueous phase was acidified with 2N hydrochloric acid and extracted with ether. The ether layer was dried over magnesium sulfate, filtered, and concentrated under vacuum to afford 23.1 g of an oil. The oil was dissolved in benzene (100 ml) and the desired product slowly deposited out of the solution as waxy crystals (9.8 g).

EXAMPLE 2 2-(2-Chloro-4-methylsulfonylbenzoyl)-4-methylthiocyclohexane-1,3-dione ##STR15##

4-Methylthiocyclohexane-1,3-dione (4.4 grams, 28 ml) and 2-chloro-4-methylsulfonylbenzoyl chloride (7.1 g, 28 mmol) were dissolved in 75 (ml) of methylene chloride at room temperature. Triethylamine (5.6 g, 56 mmol) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was dried over magnesium sulfate and then evaporated under vacuum to yield the intermediate enol ester. The enol ester was dissolved in 75 ml of acetonitrile and triethylamine (5.6 g, 56 mmol) was added all at once, followed by acetone cyanohydrin (0.8 g, 10 mmol). The reaction mixture was stirred at room temperature for 1 hour and then partitioned between 1N hydrochloric acid (100 ml) and ethyl ether (200 ml). The ether layer was washed with water and the product crystallized from the solution upon standing. Filtration of the mixture afforded 3.6 g of the desired product with a m.p. of 146°-149° C.

EXAMPLE 3 2-(2-Chloro-4-methylsulfonylbenzoyl)-4-methylsulfonylcyclohexane-1,3-dione ##STR16##

2-(2-Chloro-4-methylsulfonylbenzoyl)-4-methylthiocyclohexane-1,3-dione (1.9 g, 5 mmol) was dissolved in methylene chloride (20 ml). Meta-chloroperbenzoic acid (85%, 2.0 g, 10 mmol) was added portionwise to the stirred solution at room temperature over a period of 10 minutes. The reaction mixture was stirred at room temperature for 2 hours and then cooled to 5° C. with an ice-bath. The precipitated m-chlorobenzoic acid was removed by filtration and the product was obtained through concentration of the filtrate under vacuum. The desired product (2 g) was obtained as a tan solid with a m.p. of 175°-180° C.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I                                      __________________________________________________________________________      ##STR17##                                                                     Cmpd.                                                                          No. R  R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                             X  R.sup.6                                                                            R.sup.7                                                                             R.sup.8                                                                              m.p. °C.                    __________________________________________________________________________      1  NO.sub.2                                                                          H    H    H H H    O  C.sub.6 H.sub.5                                                                    H    H     oil                                 2  NO.sub.2                                                                          H    H    H H H    S  C.sub.6 H.sub.5                                                                    H    H     oil                                 3  NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-Cl  wax                                 4  NO.sub.2                                                                          H    H    H H H    S  C.sub.2 H.sub.5                                                                    H    4-Cl  oil                                 5a Cl H    H    H H H    S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  146-149                             6  NO.sub.2                                                                          H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl  wax                                 7  Cl H    H    H H H    S  C.sub.2 H.sub.5                                                                    H    4-SO.sub.2 CH.sub.3                                                                  oil                                 8  NO.sub.2                                                                          H    H    H H H    SO.sub.2                                                                          C.sub.2 H.sub.5                                                                    H    4-Cl  wax                                 9b Cl H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  175-180                            10  NO.sub.2                                                                          H    H    H H H    S  C.sub.2 H.sub.5                                                                    H    4-CF.sub.3                                                                           oil                                11  Cl H    H    H H H    SO.sub.2                                                                          C.sub.2 H.sub.5                                                                    H    4-SO.sub.2 CH.sub.3                                                                  wax                                12  NO.sub.2                                                                          H    H    H H H    SO.sub.2                                                                          C.sub.2 H.sub.5                                                                    H    4-CF.sub.3                                                                           semi-solid                         13  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    H      97-101                            14  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    H     175-179                            15  NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    H                                        16  NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-CF.sub.3                               17  CH.sub.3                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-SO.sub.2 C.sub.2 H.sub.5               18  Cl H    H    H H H    S  CH.sub.3                                                                           H    4-Cl                                     19  CF.sub.3                                                                          H    H    H H H    S  CH.sub.3                                                                           H    H                                        20  Cl H    H    H H H    S  CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5               21  CH.sub.3                                                                          H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 C.sub.2 H.sub.5               22  Cl H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl                                     23  CF.sub.3                                                                          H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    H                                        24  Cl H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5               25  NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                26  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           169-172                            27  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           wax                                28  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO CH.sub. 3                                                                          H    4-CF.sub.3                                                                           144-146                            29  Cl H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                30  Cl H    H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           wax                                31  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  156-159                            32  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-CF.sub.3                                                                           187-190                            33  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                34  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                35  NO.sub.2                                                                          H    H    H H H    O  CH.sub.3                                                                           H    H     oil                                36  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  123-126                            37  Cl H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  209-213                            38  Cl H    H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                39  NO.sub.2                                                                          C.sub.6 H.sub.5                                                                     H    H H H    S  CH.sub.3                                                                           H    H     oil                                40  NO.sub.2                                                                          C.sub.6 H.sub.5                                                                     H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    H     oil                                41  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-Cl  176-179                            42  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl  173-177                            43  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    4-Cl  146-149                            44  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    H     121-124                            45  NO.sub.2                                                                          H    H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                46  NO.sub.2                                                                          H    H    H H H    SO CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                47  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    H     oil                                48  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    S  CH.sub.3                                                                           H    H     oil                                49  NO.sub.2                                                                          SCH.sub.3                                                                           H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    H     oil                                50  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    H     oil                                51  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    H     134-138                            52  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO CH.sub.3                                                                           H    H     oil                                53  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-Cl  95-98                              54  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    H     198-201                            55  NO.sub.2                                                                          SO.sub.2 CH.sub.3                                                                   H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    H     glass                              56  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    S  CH.sub.3                                                                           H    4-Cl  oil                                57  NO.sub.2                                                                          SCH.sub.3                                                                           H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-Cl  oil                                58  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl  119-123                            59  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    4-Cl  oil                                60  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO CH.sub.3                                                                           H    4-Cl  oil                                61  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl  134-139                            62  NO.sub.2                                                                          CH.sub.3                                                                            SO.sub.2 CH.sub.3                                                                   H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-Cl  oil                                63  Cl CH.sub.3                                                                            H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  140-144                            64  Cl CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  159-164                            65  Cl CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                66  Cl CH.sub.3                                                                            CH.sub.3                                                                            H H H    S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                67  Cl CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO.sub.2                                                                          CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                68  Cl CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                69  Cl SCH.sub.3                                                                           H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                70  NO.sub.2                                                                          CH.sub.3                                                                            CH.sub.3                                                                            H H H    S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                71  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           3-Cl 4-SCH.sub.3                                                                          112-115                            72  Cl H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           3-Cl 4-SO.sub.2 CH.sub.3                                                                  oil                                73  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           89-92                              74  NO.sub.2                                                                          CH.sub.3                                                                            H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                75  NO.sub.2                                                                          SCH.sub.3                                                                           H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                76  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           H    4-SCH.sub.3                                                                          94-98                              77  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            O  H   H    H     semisolid                          78  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           3-Cl 4-SC.sub.2 H.sub.5                                                                   96-99                              79  Cl H    H    H H CO.sub.2 CH.sub.3                                                                   O  CH.sub.3                                                                           H    4-SO.sub.2 CH.sub.3                                                                  oil                                80  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.3                                                                           3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                           139-142                            81  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.2 Cl                                                                        H    4-CF.sub.3                                                                           124-126                            82  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.2 Cl                                                                        3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                           160-163                            83  NO.sub.2                                                                          H    H    H H CH.sub.3                                                                            S  CH.sub.2 Cl                                                                        H    H     115-117                            84  Cl H    H    H H CH.sub.3                                                                            S  CH.sub.2 Cl                                                                        3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           107-111                            85  Cl CH.sub.3                                                                            H    H H CH.sub.3                                                                            S  CH.sub.2 Cl                                                                        H    4-SO.sub.2 CH.sub.3                                                                  semisolid                          86  Cl H    H    H H CH.sub.3                                                                            SO.sub.2                                                                          CH.sub.3                                                                           3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                           190-193                            87  Cl CH.sub.3                                                                            CH.sub.3                                                                            H H H    S  CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                88  Cl CH.sub.3                                                                            CH.sub.3                                                                            H H H    SO.sub.2                                                                          CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                89c NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                90d NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           oil                                91e NO.sub.2                                                                          H    H    H H H    S  CH.sub.3                                                                           H    4-CF.sub.3                                                                           190-195                            92  Cl CH.sub.3                                                                            H    H H H    S  CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                93  Cl CH.sub.3                                                                            H    H H H    SO.sub.2                                                                          CH.sub.3                                                                           3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                __________________________________________________________________________      a Prepared in Example 2.                                                       b Prepared in Example 3.                                                       c As the triethylamine salt.                                                   d As the sodium salt.                                                          e As the copper chelate.                                                 

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Sertaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti) Indian mustard (MD) (Brassica juncea), and yellow nutsedge (YNG) (Cyperus esculentus. Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                         ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG     WO    AMG   VL    MD   YNG                                ______________________________________                                          1    30      20     10    30    100   90   80                                  2    20      30     10    0     100   100  0                                   3    100     100    100   100   100   100  80                                  4    100     100    100   100   100   100  80                                  5    100     100    30    100   100   100  80                                  6    100     100    100   100   100   100  80                                  7    90      100    90    85    100   100  80                                  8    100     100    100   95    100   100  80                                  9    100     100    95    80    100   100  70                                 10    100     100    100   100   100   100  80                                 11    100     100    20    50    100   100  40                                 12    100     100    100   100   100   100  0                                  13    100     100    100   60    100   100  30                                 14    100     100    100   90    100   100  80                                 15    100     100    100   100   100   100  80                                 16    100     100    100   100   100   100  80                                 17    100     100    90    80    100   100  30                                 18    100     100    100   100   100   100  80                                 19    100     100    100   80    100   100  30                                 20    100     100    100   100   100   100  80                                 21    100     100    10    70    100   85   40                                 22    100     100    100   100   100   100  80                                 23    100     95     100   60    100   100  50                                 24    100     100    100   100   100   100  80                                 25    90      90     10    40    100   100  80                                 26    100     100    100   100   100   100  80                                 27    100     100    100   100   100   100  80                                 28    100     100    100   85    100   100  80                                 29    100     100    100   100   100   100  80                                 30    100     100    100   100   100   100  90                                 31    100     100    20    100   100   100  80                                 32    100     100    100   90    100   100  90                                 33    100     90     50    20    100   100  80                                 34    50      50     0     40    100   100  30                                 35    100     80     50    40    100   100  80                                 36    100     100    40    100   100   100  80                                 37    100     100    90    100   100   100  80                                 38    100     100    50    100   100   100  80                                 39    100     70     30    0     80    80   0                                  40    0       0      10    0     80    100  0                                  41    100     100    100   100   100   100  80                                 42    100     100    100   10    100   100  80                                 43    100     100    100   100   100   100  80                                 44    100     100    100   60    100   100  40                                 45    100     100    100   100   100   100  85                                 46    100     100    100   100   100   100  85                                 47    100     100    100   40    100   100  80                                 48    100     100    100   20    100   100  30                                 49    100     0      0     0     0     0    0                                  50    100     100    100   80    100   100  80                                 51    100     100    100   80    100   100  80                                 52    100     85     90    10    100   95   10                                 53    100     100    100   100   100   100  80                                 54    100     100    100   80    100   100  80                                 55    0       0      0     0     0     0    0                                  56    100     100    100   80    100   100  80                                 57    60      80     60    20    100   100  20                                 58    100     100    100   90    100   100  80                                 59    100     100    100   90    100   100  80                                 60    100     100    100   95    100   100  80                                 61    100     100    100   100   100   100  80                                 62    100     30     100   30    100   100  75                                 63    100     100    100   100   100   100  80                                 64    100     100    100   100   100   100  80                                 65    100     100    100   100   100   100  80                                 66    100     100    95    100   100   100  80                                 67    100     100    100   100   100   100  70                                 68    100     100    10    70    100   100  30                                 69    100     0      0     0     100   80   0                                  70    100     100    100   100   100   100  80                                 71    100     100    100   100   100   100  80                                 72    100     100    100   100   100   100  80                                 73    100     100    100   100   100   100  80                                 74    100     100    100   100   100   100  80                                 75    0       0      0     0     80    90   0                                  76    100     100    95    100   100   100  80                                 77    100     100    100   100   100   100  80                                 78    100     100    100   100   100   100  80                                 79    100     100    50    100   100   100  80                                 80    100     100    100   100   100   100  80                                 81    100     100    100   100   100   100  80                                 82    100     100    70    80    100   100  70                                 83    100     90     90    20    100   100  30                                 84    100     100    100   100   100   100  80                                 85    100     100    85    100   100   100  80                                 86    100     100    100   100   100   100  80                                 87    100     100    95    90    100   100  0                                  88    100     100    100   100   100   100  50                                 89    100     100    100   90    100   100  80                                 90    100     100    100   100   100   100  80                                 91    100     100    80    40    100   100  10                                 92    100     100    100   100   100   100  80                                 93    100     100    100   100   100   100  80                                 ______________________________________                                    

Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III                                                        ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG     WO    AMG   VL    MD   YNG                                ______________________________________                                          1    10      20     0     20    60    30   30                                  2    100     50     20    75    100   100  10                                  3    100     100    80    80    90    100  60                                  4    100     85     90    90    90    100  70                                  5    80      85     80    90    100   100  70                                  6    100     80     80    90    95    100  70                                  7    80      80     80    80    80    100  30                                  8    100     85     80    80    100   100  30                                  9    100     90     100   80    100   100  40                                 10    100     100    85    85    90    100  30                                 11    85      95     100   90    100   100  10                                 12    100     100    100   100   100   100  90                                 13    100     100    100   100   100   100  30                                 14    100     90     100   90    100   100  30                                 15    100     100    100   85    95    90   10                                 16    100     90     85    95    95    100  60                                 17    90      85     75    60    80    60   0                                  18    70      80     20    95    95    100  0                                  19    50      30     30    90    80    20   0                                  20    100     100    90    90    85    100  10                                 21    100     100    100   90    60    60   0                                  22    85      100    80    95    95    85   60                                 23    20      20     20    60    90    85   10                                 24    100     90     85    95    95    85   30                                 25    60      75     0     80    80    80   30                                 26    60      80     80    80    80    95   30                                 27    100     90     85    100   95    100  60                                 28    95      80     80    80    80    100  60                                 29    95      85     20    90    90    90   30                                 30    100     85     80    80    85    100  30                                 31    90      80     20    85    90    85   30                                 32    95      85     90    90    90    85   30                                 33    0       75     10    60    85    100  20                                 34    0       60     0     40    80    80   0                                  35    80      80     80    60    10    100  80                                 36    100     100    100   100   100   100  80                                 37    100     10     100   85    10    100  40                                 38    100     100    100   100   100   100  50                                 39    100     50     80    90    100   100  10                                 40    10      10     10    0     0     85   0                                  41    100     100    100   100   100   100  80                                 42    100     100    100   100   100   100  90                                 43    100     100    100   100   100   100  80                                 44    100     100    100   100   100   100  30                                 45    100     100    100   100   100   100  90                                 46    100     100    100   100   100   100  85                                 47    100     100    100   100   100   100  70                                 48    100     100    100   100   100   100  30                                 49    10      0      10    0     0     0    0                                  50    100     100    100   100   100   100  80                                 51    100     100    100   100   100   100  80                                 52    100     90     100   80    100   100  10                                 53    100     100    100   100   100   100  80                                 54    100     100    100   100   100   100  80                                 55    0       0      0     0     0     0    0                                  56    100     100    100   100   100   100  70                                 57    60      50     80    20    20    50   0                                  58    100     100    100   100   100   100  90                                 59    100     100    100   100   100   100  90                                 60    100     100    90    100   100   100  30                                 61    100     100    100   100   100   100  90                                 62    100     10     80    30    80    50   0                                  63    100     100    95    90    100   100  70                                 64    100     100    100   100   100   100  30                                 65    100     100    100   100   100   100  60                                 66    100     100    100   100   100   100  30                                 67    100     100    100   100   100   100  0                                  68    70      100    80    100   100   100  20                                 69    0       20     0     20    80    80   0                                  70    80      100    90    100   100   100  30                                 71    95      100    95    100   100   100  30                                 72    100     100    95    80    100   100  0                                  73    100     100    100   100   100   100  100                                74    100     100    100   100   100   100  100                                75    0       0      0     0     100   100  0                                  76    100     100    100   100   100   100  90                                 77    100     100    100   100   100   100  70                                 78    100     100    100   100   100   100  20                                 79    100     100    90    100   100   100  30                                 80    95      90     90    100   90    100  20                                 81    100     100    100   100   100   100  100                                82    100     100    90    100   100   100  70                                 83    100     100    100   40    100   100  30                                 84    100     100    100   100   100   100  80                                 85    100     100    100   100   100   100  80                                 86    100     100    100   100   100   100  80                                 87    50      100    50    90    90    100  0                                  88    100     90     95    100   100   100  30                                 89    20      80     80    80    100   100  30                                 90    100     100    80    100   100   100  70                                 91    0       50     10    40    60    80   0                                  92    100     100    100   100   100   100  70                                 93    85      90     85    80    80    100  10                                 ______________________________________                                    

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain from about to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as destrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    ______________________________________                                         General Formula with Ranges                                                                      Specific Formula                                             ______________________________________                                         EMULSIFIABLE CONCENTRATE FORMULATION                                           Herbicidal compound                                                                        5-55      herbicidal compound                                                                           24                                        surfactant(s)                                                                              5-25      proprietary blend of                                                                          10                                        solvent(s)  20-90     oil-soluble sulfonates                                               100%      and polyoxyethylene                                                            esters                                                                         polar solvent  27                                                              petroleum hydrocarbon                                                                         39                                                                             100%                                      WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                        3-90      herbicidal compound                                                                           80                                        wetting agent                                                                              0.5-2     sodium dialkyl 0.5                                       dispersing agent                                                                           1-8       naphthalene sulfonate                                    diluent(s)  8.5-87    sodium lignosulfonate                                                                         7                                                     100%      attapulgite clay                                                                              12.5                                                                           100%                                      EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                        1-20      herbicidal compound                                                                           10                                        binding agent                                                                              0-10      lignin sulfonate                                                                              5                                         diluent(s)  70-99     calcium carbonate                                                                             85                                                    100%                     100%                                      FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                        20-70     herbicidal compound                                                                           45                                        surfactant(s)                                                                              1-10      polyoxyethylene ether                                                                         5                                         suspending agent(s)                                                                        0.05-1    attagel        0.05                                      antifreeze agent                                                                           1-10      propylene glycol                                                                              10                                        antimicrobial agent                                                                        1-10      1,2-benzisothiazoline-                                                                        0.03                                      antifoam agent                                                                             0.1- 1    3-one                                                    solvent     7.95-77.85                                                                               silicone defoamer                                                                             0.02                                                  100%      water          39.9                                                                           100%                                      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When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR18## wherein X is oxy, thio, sulfinyl or sulfonyl;R is halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C₁ -C₂ haloalkyl; R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl; trifluoromethyl or difluoromethyl; R¹ is hydrogen, C₁ -C₄ alkyl, phenyl or substituted phenyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are C₂ -C₅ alkylene; R³ is hydrogen, C₁ -C₄ alkyl with the proviso that R¹ and R³ are not both phenyl or substituted phenyl; R⁴ is hydrogen or C₁ -C₄ alkyl; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, or phenyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) --N(R^(c))C(O)R.sup. d wherein R^(c) and R^(d) are as defined; and their salts.
 2. The method of claim 1 wherein R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl, or methylsulfonyl; R¹, R², R³, R⁴ and R⁵ are hydrogen or methyl; R⁶ is hydrogen, C₁ -C₄ alkyl or phenyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N--(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 3. The method of claim 2 wherein R⁷ and R⁸ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, ethyl, or n-propyl; R^(e) C(O)-- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁷ is in the 3-position and R⁸ is in the 4-position.
 4. The method of claim 2 wherein R⁷ is hydrogen and R⁸ is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 5. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-chlorine; and X is thio.
 6. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-chlorine; and X is sulfonyl.
 7. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; and X is thio.
 8. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; and X is sulfonyl.
 9. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is methyl; R⁶ is methyl; R⁷ is hydrogen; R⁸ is 4-chlorine; and X is sulfonyl.
 10. The method of claim 1 wherein R is chlorine; R¹ is hydrogene; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is methyl; R⁷ is 3-ethoxy; R⁸ is 4--SO₂ C₂ H₅ ; and X is thio.
 11. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is ethyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; and X is thio.
 12. The method of claim 1 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is ethyl; R⁷ is hydrogen; R⁸ is 4-chloro; and X is thio.
 13. The method of claim 2 wherein R⁷ is hydrogen.
 14. The method of claim 3 wherein R⁷ is hydrogen. 